CN109721686A - A kind of modified gamma-cyclodextrin and its application in environment-friendly water-based adhesive - Google Patents
A kind of modified gamma-cyclodextrin and its application in environment-friendly water-based adhesive Download PDFInfo
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- CN109721686A CN109721686A CN201811599335.4A CN201811599335A CN109721686A CN 109721686 A CN109721686 A CN 109721686A CN 201811599335 A CN201811599335 A CN 201811599335A CN 109721686 A CN109721686 A CN 109721686A
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- cyclodextrin
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- water
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- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 49
- 239000000853 adhesive Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 58
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims abstract description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 34
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010792 warming Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 230000000844 anti-bacterial effect Effects 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000013530 defoamer Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 9
- 239000001508 potassium citrate Substances 0.000 claims description 9
- 229960002635 potassium citrate Drugs 0.000 claims description 9
- 235000011082 potassium citrates Nutrition 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- RVLJEYMXHVUVGO-UHFFFAOYSA-N 1-chloro-3-(2,3-dihydroxypropyl)-5-(hydroxymethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C(C(CO)O)N1C(=O)N(C(=O)N(C1=O)Cl)CO RVLJEYMXHVUVGO-UHFFFAOYSA-N 0.000 claims description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- RDHFYUVHVBCPIO-UHFFFAOYSA-N 2-propyl-1,3,5-triazine Chemical compound CCCC1=NC=NC=N1 RDHFYUVHVBCPIO-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 238000000889 atomisation Methods 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 244000248349 Citrus limon Species 0.000 description 8
- 235000005979 Citrus limon Nutrition 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- VYVKXVSXGURHJH-UHFFFAOYSA-N 1-propyl-1,3,5-triazinane-2,4,6-trione Chemical compound CCCN1C(=O)NC(=O)NC1=O VYVKXVSXGURHJH-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229960003975 potassium Drugs 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- -1 hydroxypropyl Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- FPGMDKDDJBEWHA-UHFFFAOYSA-N 1-(2,3-dihydroxypropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCC(O)CN1C(=O)NC(=O)NC1=O FPGMDKDDJBEWHA-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- FIMRGWGERKDGSV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate prop-1-ene Chemical class COC(C(=C)C)=O.C=CC FIMRGWGERKDGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000001034 respiratory center Anatomy 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of modified gamma-cyclodextrin and its applications in environment-friendly water-based adhesive.The modified gamma-cyclodextrin are as follows: gamma-cyclodextrin, maleic anhydride, n,N-Dimethylformamide are stirred 10-20h, 5-10h is placed after being cooled to room temperature, obtains reaction solution；Reaction solution is precipitated in chloroform, drying will be precipitated, obtains pretreatment gamma-cyclodextrin；Pretreatment gamma-cyclodextrin, nano-titanium dioxide, water are stirred 20-50min, sodium peroxydisulfate is added, is warming up to 60-90 DEG C and is stirred 2-5h, obtain mixed liquor；By mixed liquor be spray-dried to get.Compared with prior art, modification gamma-cyclodextrin of the invention is applied in environment-friendly type aqueous adhesive and its production technology, silicone acrylic emulsion, which is utilized, has the characteristics that chemical stability is good, mechanical stability is excellent, minimum film formation temperature is low, adhesive property is excellent, each raw material good dispersion in system, Aqueous Adhesives curing time of the invention is short, workability is good, water resistance is good, it is at low cost, make article shading curtain fastness is high, intensity is good, in conjunction with closely knit, and press after can quick-binding, shorten Production Time.
Description
Technical field
The present invention relates to a kind of modified gamma-cyclodextrin and its applications in environment-friendly water-based adhesive.
Background technique
Adhesive refers to the technology that homogeneous or heterogeneous surface is linked together with adhesive, and there is stress distribution to connect
The features such as continuous, light-weight, technological temperature is low.Adhesive mainly by bonding material, curing agent, toughener, diluent, filler and changes
Property agent composition.Connection of the adhesive especially suitable for different materials, different thicknesses, ultra-thin specification and complex component.Adhesive is close
For with fastest developing speed, application industry is extremely wide, is widely used in auto industry, shipbuilding industry, aerospace industries, electric work
Industry, building industry, health care industry, light and textile industries and packaging industry.There are many classification method of adhesive, can divide by application method
For thermoset, hot melt, room temperature curing type, pressure sensitive etc.；It is divided into structural, non-configuration or special glue by application；Connect shape
State can be divided into water-soluble, emulsion type, solvent type and various solid-state versions etc..
The extensive use of adhesive while bringing benefit to industrial society, also brings adverse effect, it is well known that
There are more volatile organic compounds (VOC) in adhesive, such as the organic solvent in solvent type adhesive, in three-aldehyde glue
Free formaldehyde, the styrene in unsaturated polyester (UP) adhesive, the unreacted monomer in acrylic acid ester emulsion adhesive, modified propylene
Methyl methacrylate in the fast fixing structure adhesive of acid esters, the polyisocyanates in adhesive for polyurethane, alpha-cyanoacrylate
SO2 in ester adhesive, methanol, the thickener ammonium hydroxide in acrylic acid ester emulsion etc. in 4115 building adhesives.These effumabilities
Substance be discharged into atmosphere, endanger it is very big, and some occur photochemical action, generate ozone, the ozone pollution in low layer space
Atmosphere, influences the growth of biology and the health of the mankind, some halogenated hydrocarbon solvents are then the substances for destroying atmospheric ozone layer.Some virtues
Fragrant hydrocarbon solvent toxicity is very big, or even has carcinogenicity.The steam of benzene has fragranced, but to people's strong toxicity again, sucking and warp
Skin absorption can all be poisoned, make one dizziness, headache, it is out of strength, serious when it is dead due to respiratory center spasm.
Therefore, the kind of adhesive should need to develop towards Water-borne modification, solidification, solvent free, low toxicityization direction.
Modification gamma-cyclodextrin of the invention is applied in environment-friendly type aqueous adhesive and its production technology, silicon is utilized
Acrylic emulsion has the characteristics that chemical stability is good, mechanical stability is excellent, minimum film formation temperature is low, adhesive property is excellent, each original
Material good dispersion in system, Aqueous Adhesives curing time of the invention is short, and workability is good, and water resistance is good, at low cost, makes
Article shading curtain fastness is high, intensity is good, in conjunction with closely knit, and after pressing can quick-binding, shorten Production Time.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of automobile sun blind Aqueous Adhesives and its production technologies.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of modified gamma-cyclodextrin, is prepared using following methods: by gamma-cyclodextrin, maleic anhydride, N, N- diformazan
Base formamide is stirred 10-20h, places 5-10h after being cooled to room temperature, obtains reaction solution；Reaction solution is precipitated in chloroform,
Drying will be precipitated, obtains pretreatment gamma-cyclodextrin；Pretreatment gamma-cyclodextrin, nano-titanium dioxide, water are stirred 20-
50min adds sodium peroxydisulfate, is warming up to 60-90 DEG C and is stirred 2-5h, obtains mixed liquor；Mixed liquor is spray-dried, i.e.,
?.
In one embodiment of the invention, a kind of modified gamma-cyclodextrin is prepared using following methods: by gamma-cyclodextrin,
Maleic anhydride, n,N-Dimethylformamide are stirred 10-20h, place 5-10h after being cooled to room temperature, obtain reaction solution；It will be anti-
It answers liquid to precipitate in chloroform, drying will be precipitated, obtain pretreatment gamma-cyclodextrin；Gamma-cyclodextrin, polyvinyl pyrrole will be pre-processed
Alkanone, nano-titanium dioxide, water are stirred 20-50min, add sodium peroxydisulfate, are warming up to 60-90 DEG C and are stirred 2-
5h obtains mixed liquor；By mixed liquor be spray-dried to get.
Preferably, the modification gamma-cyclodextrin, is prepared using following methods: by 200-250g gamma-cyclodextrin,
15-25g maleic anhydride, 1200-1800g N,N-dimethylformamide temperature be 75-85 DEG C with revolving speed for 500-1000r/
Min stirs 10-20h, places 5-10h after being cooled to room temperature, obtains reaction solution；Reaction solution is precipitated in chloroform, will be deposited in
Temperature is 65-75 DEG C of dry 25-35h, obtains pretreatment gamma-cyclodextrin；Will pretreatment gamma-cyclodextrin, polyvinylpyrrolidone,
Nano-titanium dioxide, water are 1:(0.02-0.06 in mass ratio): (0.01-0.05): (10-30) is with revolving speed for 300-700r/
Min is stirred 20-50min, adds the sodium peroxydisulfate of gamma-cyclodextrin weight 0.05-0.2%, is warming up to 60-90 DEG C to turn
Fast 500-1000r/min stirs 2-5h, obtains mixed liquor；By mixed liquor be spray-dried to get.
The inlet temperature of the spray drying is 170-190 DEG C, and outlet temperature is 70-85 DEG C, and hot wind wind speed is 3-5m3/
Min, feeding speed 30-60mL/min, atomizer revolving speed are 200-400r/min.
The partial size of the nano-titanium dioxide is 1~50nm.
The invention also discloses application of the above-mentioned modification gamma-cyclodextrin in environment-friendly water-based adhesive.
Concrete application is as follows:
A kind of environment-friendly water-based adhesive is made of following raw material by weight: 50-70 parts of silicone acrylic emulsion, nanometer two
5-15 parts of silica, 0.1-0.5 parts of anionic surfactant, 0.1-0.5 parts of nonionic surfactant, above-mentioned modification
4-10 parts of gamma-cyclodextrin, 0.5-1.5 parts of propylene glycol phenylate, 1-5 parts of polyvinyl alcohol, 3-9 parts of potassium citrate, organic silicon defoamer
0.1-0.3 parts, 1-3 parts of antibacterial additives, 5-15 parts of ethyl alcohol, 10-30 parts of water.Above-mentioned raw materials are weighed by weight, by the third cream of silicon
It is that 200-500r/min stirs 10-20min that liquid, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol, which are added in ethyl alcohol with revolving speed,
It is uniformly mixed, obtains component A；By nano silica, anionic surfactant, nonionic surfactant, modified γ-ring
It is that 200-500r/min stirring 10-20min is uniformly mixed that dextrin, potassium citrate, antibacterial additives, which are added to the water with revolving speed, is obtained
Component B；It is that 200-500r/min stirring 30-60min is uniformly mixed to get the environmental protection that component A, which is added in component B with revolving speed,
Aqueous Adhesives.
The anionic surfactant is aerosol-OT salt.
The nonionic surfactant is octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether.
The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazinetrione of 1-, the chloro- 3- methylol -5- (2,3- bis- of 1-
At least one of hydroxypropyl)-S- triazinetrione；Further, the Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-of 1-
S- triazinetrione, 1- chloro- 3- methylol -5- (2,3- dihydroxypropyl)-S- triazinetrione is 1:(0.4-0.6 in mass ratio)
Mixture.
The partial size of the nano silica is 1-100nm.The beneficial effects of the present invention are:
The environment-friendly type aqueous adhesive of the present invention and its production technology, be utilized silicone acrylic emulsion with chemical stability good, machine
The features such as tool excellent in stability, minimum film formation temperature are low, adhesive property is excellent, each raw material good dispersion in system, the present invention
Aqueous Adhesives curing time it is short, workability is good, and water resistance is good, at low cost, makes that article shading curtain fastness is high, intensity is good, knot
Close it is closely knit, and press after can quick-binding, shorten Production Time.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
As follows using disclosure: nano silica is the model TSP- that Jiangsu Tian Hang new material Co., Ltd provides
The nano silica of H10, primary particle size 20nm.Gamma-cyclodextrin provides for Wuxi flourishing age Hong Cheng Biotechnology Co., Ltd
Food-grade gamma-cyclodextrin.Propylene glycol phenylate, No. CAS: 6180-61-6.Polyvinyl alcohol is Renqiu City Peng Yu Chemical Co., Ltd.
The polyvinyl alcohol of the model 2488 of offer.Potassium citrate, No. CAS: 7778-49-6.Organic silicon defoamer is that Guangzhou hat will is new
The polyether silicones defoaming agent for the model CX-470 that material Science and Technology Ltd. provides.Ethyl alcohol, No. CAS: 64-17-5.Sulfonation
Dioctyl succinate sodium salt is provided by Jiangsu Hai'an Petrochemical Plant, model OT.Nonylphenol polyoxyethylene ether is Shandong person of outstanding talent
The nonylphenol polyoxyethylene ether for the model TX-10 that credit new material Co., Ltd provides.Chloro- 3- methylol -5- (2, the 3- dihydroxies of 1-
Base propyl)-S- triazinetrione prepared according to method shown in embodiment 3 in the Chinese patent application No. is 201310016639.4.
Maleic anhydride, No. CAS: 108-31-6.N,N-Dimethylformamide, No. CAS: 68-12-2.Chloroform, No. CAS: 67-66-3.It is poly-
Vinylpyrrolidone is the polyvinylpyrrolidone for the model PVPK30 that Shandong Ge Fengrui new material Co., Ltd provides.1-
Chloro- 3,5- diepoxy propyl-S- triazinetrione is according in the Chinese patent application No. is 201210362485.X shown in embodiment 2
Method preparation.Nano-titanium dioxide is the nanometer titanium dioxide for the model TTP-A10 that Jiangsu Tian Hang new material Co., Ltd provides
Titanium, primary particle size 10nm.Sodium peroxydisulfate, No. CAS: 7775-27-1.Silicone acrylic emulsion is according to application No. is 200810045627.3
Chinese patent in the preparation of method shown in specific embodiment.
Embodiment 1
The production technology of environment-friendly type aqueous adhesive, comprising the following steps:
S1, each raw material: 60 parts of silicone acrylic emulsion, 8 parts of nano silica, aerosol-OT is weighed by weight
0.25 part of salt, 0.25 part of nonylphenol polyoxyethylene ether, modified 7 parts of gamma-cyclodextrin, 1 part of propylene glycol phenylate, 3 parts of polyvinyl alcohol, lemon
6 parts of lemon acid potassium, 0.15 part of organic silicon defoamer, 1.5 parts of antibacterial additives, 10 parts of ethyl alcohol, 20 parts of water；
S2, silicone acrylic emulsion, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol are added in ethyl alcohol with revolving speed is 300r/
Min stirs 15min and is uniformly mixed, and obtains component A；By nano silica, anionic surfactant, non-ionic surface active
Agent, modified gamma-cyclodextrin, potassium citrate, antibacterial additives, which are added to the water, stirs 15min mixing for 300r/min with revolving speed
It is even, obtain component B；It is that 300r/min stirring 40min is uniformly mixed to get environment-friendly type water that component A, which is added in component B with revolving speed,
Property adhesive.
The modified gamma-cyclodextrin the preparation method comprises the following steps: by 230g gamma-cyclodextrin, 20g maleic anhydride, 1500g N, N-
Dimethylformamide temperature be 80 DEG C with revolving speed be 600r/min stirring 12h, place 8h after being cooled to room temperature, reacted
Liquid；Reaction solution is precipitated in chloroform, will be deposited in temperature is 70 DEG C of dry 30h, obtains pretreatment gamma-cyclodextrin；It will locate in advance
Reason gamma-cyclodextrin, polyvinylpyrrolidone, nano-titanium dioxide, water are that 1:0.04:0.03:20 is with revolving speed in mass ratio
500r/min is stirred 30min, adds the sodium peroxydisulfate of gamma-cyclodextrin weight 0.1%, is warming up to 70 DEG C with revolving speed
600r/min stirs 3.5h, obtains mixed liquor；Mixed liquor is spray-dried, the inlet temperature of the spray drying is 180 DEG C, out
Mouth temperature is 75 DEG C, and hot wind wind speed is 4m3/ min, feeding speed 50mL/min, atomizer revolving speed are 300r/min；Change to obtain the final product
Property gamma-cyclodextrin.
The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazinetrione of 1-.
Embodiment 2
The production technology of environment-friendly type aqueous adhesive, comprising the following steps:
S1, each raw material: 60 parts of silicone acrylic emulsion, 8 parts of nano silica, aerosol-OT is weighed by weight
0.25 part of salt, 0.25 part of nonylphenol polyoxyethylene ether, 7 parts of gamma-cyclodextrin, 1 part of propylene glycol phenylate, 3 parts of polyvinyl alcohol, citric acid
6 parts of potassium, 0.15 part of organic silicon defoamer, 1.5 parts of antibacterial additives, 10 parts of ethyl alcohol, 20 parts of water；
S2, silicone acrylic emulsion, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol are added in ethyl alcohol with revolving speed is 300r/
Min stirs 15min and is uniformly mixed, and obtains component A；By nano silica, anionic surfactant, non-ionic surface active
Agent, modified gamma-cyclodextrin, potassium citrate, antibacterial additives, which are added to the water, stirs 15min mixing for 300r/min with revolving speed
It is even, obtain component B；It is that 300r/min stirring 40min is uniformly mixed to get environment-friendly type water that component A, which is added in component B with revolving speed,
Property adhesive.
The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazinetrione of 1-.
Embodiment 3
The production technology of environment-friendly type aqueous adhesive, comprising the following steps:
S1, each raw material: 60 parts of silicone acrylic emulsion, 8 parts of nano silica, aerosol-OT is weighed by weight
0.25 part of salt, 0.25 part of nonylphenol polyoxyethylene ether, modified 7 parts of gamma-cyclodextrin, 1 part of propylene glycol phenylate, 3 parts of polyvinyl alcohol, lemon
6 parts of lemon acid potassium, 0.15 part of organic silicon defoamer, 1.5 parts of antibacterial additives, 10 parts of ethyl alcohol, 20 parts of water；
S2, silicone acrylic emulsion, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol are added in ethyl alcohol with revolving speed is 300r/
Min stirs 15min and is uniformly mixed, and obtains component A；By nano silica, anionic surfactant, non-ionic surface active
Agent, modified gamma-cyclodextrin, potassium citrate, antibacterial additives, which are added to the water, stirs 15min mixing for 300r/min with revolving speed
It is even, obtain component B；It is that 300r/min stirring 40min is uniformly mixed to get environment-friendly type water that component A, which is added in component B with revolving speed,
Property adhesive.
The modified gamma-cyclodextrin the preparation method comprises the following steps: by 230g gamma-cyclodextrin, 20g maleic anhydride, 1500g N, N-
Dimethylformamide temperature be 80 DEG C with revolving speed be 600r/min stirring 12h, place 8h after being cooled to room temperature, reacted
Liquid；Reaction solution is precipitated in chloroform, will be deposited in temperature is 70 DEG C of dry 30h, obtains pretreatment gamma-cyclodextrin；It will locate in advance
It with revolving speed is that 500r/min is stirred 30min that reason gamma-cyclodextrin, nano-titanium dioxide, water are 1:0.03:20 in mass ratio,
The sodium peroxydisulfate for adding gamma-cyclodextrin weight 0.1% is warming up to 70 DEG C and stirs 3.5h with revolving speed 600r/min, mixed
Liquid；Mixed liquor is spray-dried, the inlet temperature of the spray drying is 180 DEG C, and outlet temperature is 75 DEG C, and hot wind wind speed is
4m3/ min, feeding speed 50mL/min, atomizer revolving speed are 300r/min；Up to modified gamma-cyclodextrin.
The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazinetrione of 1-.
Embodiment 4
The production technology of environment-friendly type aqueous adhesive, comprising the following steps:
S1, each raw material: 60 parts of silicone acrylic emulsion, 8 parts of nano silica, aerosol-OT is weighed by weight
0.25 part of salt, 0.25 part of nonylphenol polyoxyethylene ether, modified 7 parts of gamma-cyclodextrin, 1 part of propylene glycol phenylate, 3 parts of polyvinyl alcohol, lemon
6 parts of lemon acid potassium, 0.15 part of organic silicon defoamer, 1.5 parts of antibacterial additives, 10 parts of ethyl alcohol, 20 parts of water；
S2, silicone acrylic emulsion, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol are added in ethyl alcohol with revolving speed is 300r/
Min stirs 15min and is uniformly mixed, and obtains component A；By nano silica, anionic surfactant, non-ionic surface active
Agent, modified gamma-cyclodextrin, potassium citrate, antibacterial additives, which are added to the water, stirs 15min mixing for 300r/min with revolving speed
It is even, obtain component B；It is that 300r/min stirring 40min is uniformly mixed to get environment-friendly type water that component A, which is added in component B with revolving speed,
Property adhesive.
The modified gamma-cyclodextrin the preparation method comprises the following steps: by 230g gamma-cyclodextrin, 20g maleic anhydride, 1500g N, N-
Dimethylformamide temperature be 80 DEG C with revolving speed be 600r/min stirring 12h, place 8h after being cooled to room temperature, reacted
Liquid；Reaction solution is precipitated in chloroform, will be deposited in temperature is 70 DEG C of dry 30h, obtains pretreatment gamma-cyclodextrin；It will locate in advance
Reason gamma-cyclodextrin, polyvinylpyrrolidone, nano-titanium dioxide, water are that 1:0.04:0.03:20 is with revolving speed in mass ratio
500r/min is stirred 30min, adds the sodium peroxydisulfate of gamma-cyclodextrin weight 0.1%, is warming up to 70 DEG C with revolving speed
600r/min stirs 3.5h, obtains mixed liquor；Mixed liquor is spray-dried, the inlet temperature of the spray drying is 180 DEG C, out
Mouth temperature is 75 DEG C, and hot wind wind speed is 4m3/ min, feeding speed 50mL/min, atomizer revolving speed are 300r/min；Change to obtain the final product
Property gamma-cyclodextrin.
The Antibacterial accessory ingredient is the chloro- 3- methylol -5- of 1- (2,3- dihydroxypropyl)-S- triazinetrione.
Embodiment 5
The production technology of environment-friendly type aqueous adhesive, comprising the following steps:
S1, each raw material: 60 parts of silicone acrylic emulsion, 8 parts of nano silica, aerosol-OT is weighed by weight
0.25 part of salt, 0.25 part of nonylphenol polyoxyethylene ether, modified 7 parts of gamma-cyclodextrin, 1 part of propylene glycol phenylate, 3 parts of polyvinyl alcohol, lemon
6 parts of lemon acid potassium, 0.15 part of organic silicon defoamer, 1.5 parts of antibacterial additives, 10 parts of ethyl alcohol, 20 parts of water；
S2, silicone acrylic emulsion, propylene glycol phenylate, organic silicon defoamer, polyvinyl alcohol are added in ethyl alcohol with revolving speed is 300r/
Min stirs 15min and is uniformly mixed, and obtains component A；By nano silica, anionic surfactant, non-ionic surface active
Agent, modified gamma-cyclodextrin, potassium citrate, antibacterial additives, which are added to the water, stirs 15min mixing for 300r/min with revolving speed
It is even, obtain component B；It is that 300r/min stirring 40min is uniformly mixed to get environment-friendly type water that component A, which is added in component B with revolving speed,
Property adhesive.
The modified gamma-cyclodextrin the preparation method comprises the following steps: by 230g gamma-cyclodextrin, 20g maleic anhydride, 1500g N, N-
Dimethylformamide temperature be 80 DEG C with revolving speed be 600r/min stirring 12h, place 8h after being cooled to room temperature, reacted
Liquid；Reaction solution is precipitated in chloroform, will be deposited in temperature is 70 DEG C of dry 30h, obtains pretreatment gamma-cyclodextrin；It will locate in advance
Reason gamma-cyclodextrin, polyvinylpyrrolidone, nano-titanium dioxide, water are that 1:0.04:0.03:20 is with revolving speed in mass ratio
500r/min is stirred 30min, adds the sodium peroxydisulfate of gamma-cyclodextrin weight 0.1%, is warming up to 70 DEG C with revolving speed
600r/min stirs 3.5h, obtains mixed liquor；Mixed liquor is spray-dried, the inlet temperature of the spray drying is 180 DEG C, out
Mouth temperature is 75 DEG C, and hot wind wind speed is 4m3/ min, feeding speed 50mL/min, atomizer revolving speed are 300r/min；Change to obtain the final product
Property gamma-cyclodextrin.
The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazinetrione of 1-, the chloro- 3- methylol -5- (2,3- bis- of 1-
Hydroxypropyl)-S- triazinetrione is mixture that 1:0.5 is mixed in mass ratio.
Test case 1
The environment-friendly type aqueous adhesive using modified gamma-cyclodextrin in embodiment 1-5 is tested for the property.Specific knot
Fruit is shown in Table 1.
Glue film water resistance test: the environment-friendly type aqueous adhesive that embodiment is prepared is in smooth clean polytetrafluoroethyl-ne
Casting film-forming on alkene plate continues in 25 DEG C of placements, three days drying and forming-films, then in 50 DEG C, the vacuum oven that vacuum degree is 130Pa
It is 12 hours dry, film thickness 2mm.Glue film is cut to the sample of 30mm × 30mm, it is 12 hours dry in 50 DEG C of vacuum ovens,
Claim quality to obtain m1, be soaked in 20 DEG C of deionized waters for 24 hours, taking-up claims quality to obtain m2 after quickly blotting surface moisture content with filter paper, inhales
Water rate (%)=[(m2-m1)/m1] × 100%.
Anti-microbial property: GB/T21866-2008 antibiotic paint anti-microbial property measuring method and antibacterial effect, HG/T are pressed
The measurement of 3980-2007 antibiotic paint, tests strain: Candida albicans (ATCC10231).
Anti-light illumination aging performance test:
1, prepared by glue film: the environment-friendly type aqueous adhesive that embodiment is prepared is in smooth clean polyfluortetraethylene plate
Upper casting film-forming continues drying in 25 DEG C of placements, three days drying and forming-films, then in 50 DEG C, the vacuum oven that vacuum degree is 130Pa
12 hours, film thickness 2mm.
2, ultraviolet lighting aging process: film sample is fixed on the specimen holder of ultraviolet accelerated ageing lamp box, in lamp box
Operating temperature be 45 DEG C.Artificial ultraviolet ageing experiment is carried out to sample, irradiation time is 400 hours.The test of ultraviolet lamp box
Condition is as follows:
(1) working size: 450 × 1170 × 500mm；
(2) size of sample: 150 × 75mm；
(3) fluorescent tube spacing: 35mm；
(4) sample and fluorescent tube distance: 50mm；
(5) ultraviolet wavelength: 340nm；
(6) power: 40W × 6；
(7) irradiation: 40W/cm2。
3, tensile strength is tested: glue film being frustrated knife cutting with standard and grows into 20mm, the dumbbell shape batten of wide 4mm, in temperature
Under conditions of degree is 25 DEG C, relative humidity is 60%, sample is placed 24 hours, with Zwick/Roell Z020 type universal material
Testing machine (German Zwick company) measures the tensile strength of glue film, tensile speed 150mm/min.Test glue film ultraviolet lighting
The forward and backward tensile strength of aging process.Tensile strength reduced rate (%)=(tensile strength-ultraviolet lighting before ultraviolet lighting aging
Aging post-tensioning intensity) tensile strength × 100 before/ultraviolet lighting aging.
Table 1: test result table
Modified gamma-cyclodextrin provided by the invention, handles gamma-cyclodextrin, later by with nano-titanium dioxide
Graft modification enhances the resistance to light and antiseptic property of adhesive.Above embodiment is only preferred implementation of the invention
Mode, the scope of protection of the present invention is not limited thereto, and what those skilled in the art was done on the basis of the present invention appoints
The variation and replacement of what unsubstantiality belong to scope of the present invention.
Claims (7)
1. a kind of modified gamma-cyclodextrin, which is characterized in that be prepared using following methods: by gamma-cyclodextrin, maleic anhydride,
N,N-Dimethylformamide is stirred 10-20h, places 5-10h after being cooled to room temperature, obtains reaction solution；By reaction solution in chlorine
Precipitating, will precipitate drying in imitative, obtain pretreatment gamma-cyclodextrin；It will pretreatment gamma-cyclodextrin, nano-titanium dioxide, water stirring
20-50min is mixed, sodium peroxydisulfate is added, is warming up to 60-90 DEG C and is stirred 2-5h, obtain mixed liquor；Mixed liquor is sprayed
It is dry to get.
2. a kind of modified gamma-cyclodextrin, which is characterized in that be prepared using following methods: by gamma-cyclodextrin, maleic anhydride,
N,N-Dimethylformamide is stirred 10-20h, places 5-10h after being cooled to room temperature, obtains reaction solution；By reaction solution in chlorine
Precipitating, will precipitate drying in imitative, obtain pretreatment gamma-cyclodextrin；Gamma-cyclodextrin, polyvinylpyrrolidone, nanometer will be pre-processed
Titanium dioxide, water are stirred 20-50min, add sodium peroxydisulfate, are warming up to 60-90 DEG C and are stirred 2-5h, are mixed
Liquid；By mixed liquor be spray-dried to get.
3. modified gamma-cyclodextrin as claimed in claim 2, it is characterised in that: be prepared using following methods: by 200-
250g gamma-cyclodextrin, 15-25g maleic anhydride, 1200-1800g N,N-dimethylformamide are 75-85 DEG C with revolving speed in temperature
10-20h is stirred for 500-1000r/min, 5-10h is placed after being cooled to room temperature, obtains reaction solution；Reaction solution is sunk in chloroform
It forms sediment, will be deposited in temperature is 65-75 DEG C of dry 25-35h, obtains pretreatment gamma-cyclodextrin；Gamma-cyclodextrin, poly- second will be pre-processed
Alkene pyrrolidone, nano-titanium dioxide, water are 1:(0.02-0.06 in mass ratio): (0.01-0.05): (10-30) is with revolving speed
300-700r/min is stirred 20-50min, adds the sodium peroxydisulfate of gamma-cyclodextrin weight 0.05-0.2%, is warming up to
60-90 DEG C is stirred 2-5h with revolving speed 500-1000r/min, obtains mixed liquor；By mixed liquor be spray-dried to get.
4. the modification gamma-cyclodextrin as described in claims 1 or 2 or 3, it is characterised in that: the inlet temperature of the spray drying
It is 170-190 DEG C, outlet temperature is 70-85 DEG C, and hot wind wind speed is 3-5m3/ min, feeding speed 30-60mL/min, atomization
Machine revolving speed is 200-400r/min.
5. the modification gamma-cyclodextrin as described in claims 1 or 2 or 3, it is characterised in that: the partial size of the nano-titanium dioxide
For 1~50nm.
6. application of the modified gamma-cyclodextrin as claimed in any one of claims 1 to 5 in environment-friendly water-based adhesive.
7. application as claimed in claim 6, which is characterized in that the environment-friendly water-based adhesive is by following original by weight
Material composition: 50-70 parts of silicone acrylic emulsion, 5-15 parts of nano silica, 0.1-0.5 parts of anionic surfactant, nonionic table
Activating agent 0.1-0.5 parts of face, 4-10 parts of modification gamma-cyclodextrin, propylene glycol phenylate 0.5-1.5 as described in Claims 1 to 5
Part, 1-5 parts of polyvinyl alcohol, 3-9 parts of potassium citrate, 0.1-0.3 parts of organic silicon defoamer, 1-3 parts of antibacterial additives, ethyl alcohol 5-15
Part, 10-30 parts of water；The anionic surfactant is aerosol-OT salt；The nonionic surfactant
For octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether；The Antibacterial accessory ingredient is chloro- 3, the 5- diepoxy propyl-S- triazine of 1-
At least one of triketone, 1- chloro- 3- methylol -5- (2,3- dihydroxypropyl)-S- triazinetrione.
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